WO2002036701A1

WO2002036701A1 - Object having a microbicide coating, method for the production thereof and use of the same

Info

Publication number: WO2002036701A1
Application number: PCT/EP2001/008167
Authority: WO
Inventors: Thomas Schiestel; Hermann Schirra; Helmut Schmidt; Detmar Buxmann
Original assignee: Institut Für Neue Materialien Gem. Gmbh; Ursapharm Arzneimittel Gmbh & Co. Kg
Priority date: 2000-11-02
Filing date: 2001-07-13
Publication date: 2002-05-10
Also published as: JP4889188B2; EP1330501A1; EP1330501B1; JP2004512940A; EP1330501B8; ES2253402T3; US20040029834A1; KR20040030449A; CN1308406C; US7279173B2; DE50108405D1; AU2001276405A1; DK1330501T3; CN1633484A; DE10054248A1; KR100763696B1; ATE312887T1

Abstract

The invention relates to an object having a microbicide coating, especially a container, at least part of said object being coated with an organically modified, inorganic matrix containing a silver colloid. Said coating can be obtained by applying a coating composition comprising a) a hydrolyzate or a condensate based on at least one hydrolyzable silane consisting of at least one non-hydrolyzable substituent, and b) a silver compound, to the surface of the object, followed by heat treatment and/or radiation treatment to form a coating containing a silver colloid. The inventive coated objects are especially suitable for disinfecting, preservation, cosmetic, pharmaceutical, or medical purposes. Preferred areas of application are pharmaceutical or medical objects, especially containers for medicaments, or objects or components which come into contact with the human body and which need sterilising.

Description

MICROBICIDALLY COATED OBJECT, METHOD FOR THE PRODUCTION AND USE THEREOF

The present invention relates to microbicid-coated articles, in particular containers, the coating of which has an organically modified inorganic matrix containing silver colloids, a process for their production and the use for disinfectant, preservative or medical purposes.

It is known that silver ions have a strong microbicidal effect. The microbicidal action of the silver ions is also evident when silver-containing compounds in a matrix, e.g. a polymer matrix with a sufficient free volume are present and even if silver colloids are incorporated into a matrix. A sufficient rate of diffusion of silver ions to the surface is necessary. The silver can e.g. in the form of soluble compounds in lacquer solutions or in the form of solutions containing silver colloid in order to obtain microbicidal coatings.

Soluble silver compounds generally have the disadvantage that they diffuse relatively quickly and their action is exhausted relatively quickly, especially when there is contact with solutions. The silver colloids can be mixed into a coating composition to produce silver colloid-containing coating compositions. However, this has the general disadvantage that stable silver colloid solutions are necessary, the stability of which generally has to be achieved by electrostatic stabilization (pH stabilization), i.e. Protic solvents are required and certain pH values have to be set so that the addition of silver colloids is not possible for many coating systems.

In another method, silver colloids are produced in a coating composition made of glass-forming elements from silver compounds in situ during the coating process, so that coatings are obtained that contain silver colloids in a glass matrix. The disadvantage of this method, however, is that brittle coatings are formed and very high temperatures are required to form the glass matrix containing silver colloid. This method is therefore unsuitable for the coating of temperature-sensitive objects.

The invention has for its object to be able to provide temperature-sensitive objects with a silver colloid-containing coating, silver colloids generated in situ can be produced even at relatively low temperatures and the coating can also be cured at relatively low temperatures. At the same time, larger colloids should be possible because they have a high long-term effect. In addition, a coating with high elasticity should be possible, which is also applicable to objects with a flexible surface.

Surprisingly, these requirements are met by the microbicide-coated article, in particular a container, of the present invention, a coating with an organically modified inorganic matrix containing silver colloids being present on at least part of the article, which coating can be obtained by applying a coating composition comprising a) a hydrolyzate or condensate based on at least one hydrolyzable silane with at least one non-hydrolyzable substituent and b) a silver compound, on the surface of the article and treatment with heat and / or radiation to form the silver colloid-containing coating.

Another object of the present invention is a method for producing a microbicidal coated object with a silver colloid-containing coating which has an organically modified inorganic matrix, in which a coating composition comprising a) a hydrolyzate or condensate based on at least one hydrolyzable silane with at least not one hydrolyzable substituents and b) applying a silver compound to at least part of the surface of the article and treating it with heat and / or radiation to form the silver colloid-containing coating.

The object of the invention enables coatings containing silver colloid to be obtained at low temperatures, so that they are suitable for temperature-sensitive objects. A high elasticity of the layer enables a coating of flexible objects. The objects coated according to the invention are notable for a strong microbicidal action.

The object to be coated can be any object. Because of the microbicidal action, the objects coated according to the invention are particularly suitable for disinfectant, preservative, cosmetic or pharmaceutical or medical purposes. For items in the pharmaceutical or medical field, e.g. The present invention is particularly suitable for coated containers for pharmaceuticals or for objects or components which come into contact with the human body and are intended to remain germ-free.

It is therefore preferably an object for storing solid (for example ointment-like), liquid or gaseous media, in particular for storing liquid media, for example solutions. The containers can be, for example, bottles, vials, ampoules, (sealable) bags, packaging such as blisters, cans, spray bottles or cans and tubes. The media to be stored are in particular pharmaceuticals, preferably in liquid form, for example as a solution, or other media used in the medical field, for example isotonic saline solutions and storage or cleaning agents for contact lenses. Containers for nasal sprays and eye drops are particularly preferred. Of course, the containers can also be used in other fields. Other preferred objects which are coated according to the invention are objects or devices or parts thereof used in the medical field, for example surgical instruments, trays and tubes.

The article can be fully or partially coated. For example, it may be appropriate to coat containers such as drug bottles only on the inner surfaces, while the outer surface remains uncoated. The article may consist of one or more materials, e.g. Different components of the object can consist of different materials.

The object to be coated or the part of the object to be coated (substrate) can be made of any material, e.g. B. made of metal, glass, ceramic, glass ceramic, plastic or paper. Since a particular advantage of the present invention is that coatings containing silver colloid can be obtained without having to use high temperatures, the invention is particularly suitable for thermally sensitive objects. Objects or parts of objects made of plastic are therefore preferably used. Examples of plastics are polyethylene, polypropylene, polyacrylate, such as polymethyl methacrylate and polymethylacrylate, polyvinyl butyral, polycarbonate, polyurethanes, ABS copolymers or polyvinyl chloride, with polyethylene being particularly preferred. The article can be pretreated in the usual way, e.g. B. to achieve cleaning, degreasing or better adhesion with the coating. Of course, the part of the object to be coated can first be coated separately as a substrate and then combined to form the finished object.

The coating composition used comprises a) a hydrolyzate or condensate based on at least one hydrolyzable silane with at least one non-hydrolyzable (carbon-containing) substituent and b) a silver compound. The hydrolyzate or condensate is preferably partially hydrated. lysis or condensation of one or more silanes of the general formula (I)

R _a SiX _(4. _a) (I)

obtained in which the radicals R are identical or different and represent non-hydrolyzable groups, the radicals X are identical or different and represent hydrolyzable groups or hydroxyl groups and a is 1, 2 or 3, a value of 1 being preferred.

In the case of organosilanes of the formula (I) the hydrolysable groups X are, for example, hydrogen or halogen (F, Cl, Br or I, especially Cl and Br), alkoxy (preferably C ,. ₆ alkoxy, in particular C ^ alkoxy, such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, sec-butoxy and tert-butoxy), aryl oxy (preferably _C6. _10, aryloxy, such as phenoxy), acyloxy ( preferably C ,. ₆ acyl oxy, such as acetoxy or propionyloxy), alkylcarbonyl (preferably C _2. _7, alkyl carbonyl such as acetyl), amino, monoalkylamino or dialkylamino wherein the alkyl groups are preferably 1 to 12, in particular 1 have up to 6 carbon atoms. Preferred hydrolyzable radicals are halogen, alkoxy groups and acyloxy groups. Particularly preferred hydrolyzable radicals are alkoxy groups, especially methoxy and ethoxy.

R is a non-hydrolyzable organic radical that can optionally carry a functional group. Examples of R are alkyl (preferably C ^ alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl and t-butyl, pentyl, hexyl or cyclohexyl), alkenyl (preferably C _2. ₆ - alkenyl groups such as vinyl, 1-propenyl, 2-propenyl and butenyl), alkynyl (preferably C _2. _6, alkynyl such as acetylenyl and propargyl) and aryl (preferably C _6. _10, aryl, such as phenyl and naphthyl).

Specific examples of functional groups of the radical R are, in addition to the groups with unsaturated CC bonds already mentioned above, the epoxy, Hydroxy, ether, amino, monoalkylamino, dialkylamino, for example with the C ₆ alkyl groups defined above, amide, carboxy, mercapto, thioether, vinyl, isocyanate, acryloxy, Methacryloxy, acid anhydride, acid halide, cyano, halogen, aldehyde, alkylcarbonyl, sulfonic acid and phosphoric acid groups. These functional groups are bonded to the silicon atom via alkylene, alkenylene or arylene bridge groups, which can be interrupted by oxygen or sulfur atoms or -NH groups. The bridging groups mentioned are derived, for example, from the alkyl, alkenyl or aryl radicals mentioned above. The radicals R preferably contain 1 to 18, in particular 1 to 8, carbon atoms. The radicals R and X mentioned can optionally have one or more customary substituents, such as halogen or alkoxy.

At least one of the hydrolyzable silanes used with at least one non-hydrolyzable substituent on the non-hydrolyzable substituent preferably contains one of the functional groups mentioned above. Organic crosslinking can then take place via this functional group, e.g. by reaction of the functional groups on the silanes with one another, where different or identical functional groups can react with one another, or with functional groups on the organic compounds described below, which may also be present in the coating composition.

Preferred functional groups are the epoxy, acid anhydride and amino groups, a combination of at least one hydrolyzable silane which has one or more epoxy groups on at least one non-hydrolyzable substituent and at least one hydrolyzable silane which has on at least one non-hydrolyzable substituent has one or more amino groups, is particularly preferred. A combination is very particularly preferred which, in addition to an epoxy silane and an aminosilane, additionally contains at least one hydrolyzable silane which has one or more acid anhydride groups on at least one non-hydrolyzable substituent. In the preferred epoxy silanes of the general formula (I) above, a has a value of 1, X is preferably C - ^ - alkoxy, particularly preferably methoxy and ethoxy, and R is a non-hydrolyzable radical having at least one epoxy group, e.g. B. an aliphatic, cycloaliphatic or aromatic radical, especially alkylene, for. B. C ₁ -C ₆ alkylene, such as methylene, ethylene, propylene and butylene, with at least one epoxy group. The radical R is preferably a glycidyloxy (C ₁ ^) alkylene radical. Specific examples are ß-glycidyloxyethyl, γ-glycidyloxypropyl, δ-glycidyloxybutyl, ε-glycidyloxypentyl, ω-glycidyloxyhexyl, and 2- (3,4-epoxycyclohexyl) ethyl. Epoxy silanes used with particular preference are γ-glycidyloxypropyltrimethoxysilane (GPTS) and γ-glycidyloxypropyltriethoxysilane (GPTES).

Preferred aminosilanes are those of the general formula (I) above, in which a has a value of 1, X is preferably C 1-4 alkoxy, particularly preferably methoxy and ethoxy, and R is a non-hydrolyzable radical having at least one amino group, e.g. B. an aliphatic, cycloaliphatic or aromatic radical, especially alkylene, for. B. C _r C ₆ alkylene, such as methylene, ethylene, propylene and butylene, with at least one primary, secondary or tertiary amino group. For example, R is an R ¹ ₂ N- (alkylene-NR ¹ ) _x -alkylene radical, where x is 0 to 5, the alkylene groups may be the same or different and in particular may be those mentioned above, and R ^{1 is the} same or different and hydrogen or an optionally substituted alkyl radical, for example those mentioned in the general formula (I) above. R ¹ can also be a divalent radical, for example alkylene, to form a heterocyclic ring. If appropriate, a further non-hydrolyzable radical, for example alkyl, can also be present (a = 2). Specific examples of such silanes are 3-aminopropyltrimethoxysilane (APTS), 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3- aminopropyltrimethoxysilane, N- [N '- (2 ^, -aminoethyl) -2-aminoethyl] -3-aminopropyltri - methoxysilane, N- [3- (triethoxysilyl) propyl] -4,5-dihydroimidazole and [N- (2-aminoethyl) -3- aminopropylj-methyldiethoxysilane. 3-Aminopropyltrimethoxysilane (APTS) is particularly preferred. Preferred anhydride silanes are those of the above general formula (I), in which a has a value of 1, X is preferably C 1-4 alkoxy, particularly preferably methoxy and ethoxy, and R is a non-hydrolyzable radical having at least one anhydride group, e.g. B. an aliphatic, cycloaliphatic or aromatic radical, especially alkylene, for. B. C, -C ₈ alkylene, especially CC ₄ alkylene, such as methylene, ethylene, propylene and butylene, with an anhydride group. In the anhydride group, which, like the epoxy group, is capable of condensation with amino groups, it can, for. B. are radicals which are derived from carboxylic anhydrides, such as succinic anhydride, maleic anhydride or phthalic anhydride, which are bonded to the silicon atom via one of the abovementioned radicals, in particular C ₁ -C ₄ -alkylene. Examples are [3- (triethoxysilyl) propyl] succinic anhydride (dihydro-3- (3-triethoxysilyl) propyl) -2,5-furandione, GF20) and [3- (trimethoxysilyl) propyl] succinic anhydride.

If appropriate, hydrolyzable silanes or precondensates thereof can also be used, which at least partially have organic radicals which are substituted with fluorine. For this purpose, for example, hydrolyzable silicon compounds of the general formula (I) can be used with at least one non-hydrolyzable radical R which, for example, has on average 2 to 30 fluorine atoms bonded to carbon atoms, which are preferably separated from Si by at least two atoms. As hydrolyzable groups z. B. those are used, as indicated in formula (I) for X. Specific examples of fluorosilanes are C ₂ F ₅ - CH ₂ CH ₂ -SiZ ₃ , nC ₆ F ₁₃ -CH ₂ CH ₂ -SiZ ₃ , nC ₈ F ₁₇ -CH ₂ CH ₂ -SiZ ₃ , nC ₁₀ F ₂₁ -CH ₂ CH ₂ -SiZ ₃ with Z = OCH ₃ , OC ₂ H ₅ or Cl, iC ₃ F ₇ O-CH ₂ CH ₂ CH ₂ -SiCI ₂ (CH ₃ ), nC ₆ F ₁₃ -CH ₂ CH ₂ - SiCI ₂ (CH ₃ ) and nC ₆ F ₁₃ -CH ₂ CH ₂ -SiCI (CH ₃ ) ₂ . The use of such a fluorinated silane means that the corresponding coating is additionally given hydrophobic and oleophobic properties. Such silanes are described in detail in DE 4118184. The proportion of fluorinated silanes is preferably not more than 0.5 to 2% by weight, based on the total organically modified inorganic polycondensate used. Of the hydrolyzable silanes used with at least one non-hydrolyzable substituent for the hydrolyzate or condensate, at least 40 mol%, preferably at least 70 mol%, particularly preferably at least 90 mol%, have at least one functional group on at least one non-hydrolyzable substituent , In a preferred embodiment, all hydrolyzable silanes used have at least one functional group with at least one non-hydrolyzable substituent on at least one non-hydrolyzable substituent. When epoxy silane, aminosilane and anhydride silane are used in combination, the ratio of epoxy silane / aminosilane / anhydride silane is preferably 0.5 to 1.5 / 1 to 3/1 to 3, based on the functional groups.

For the preparation of the hydrolyzate or condensate, further hydrolyzable compounds of an element M can optionally be used as matrix formers. These are in particular compounds of at least one element M from the main groups III to V and / or the subgroups II to IV of the periodic table of the elements. They are preferably hydrolyzable compounds of Si, Al, B, Sn, Ti, Zr, V or Zn, in particular those of Si, Al, Ti or Zr, or mixtures of two or more of these elements. It should be noted that other hydrolyzable compounds can of course also be used, in particular those of elements of main groups I and II of the periodic table (eg Na, K, Ca and Mg) and of subgroups V to VIII of the periodic table (eg Mn, Cr, Fe and Ni). Hydrolyzable compounds of the lanthanides can also be used. These hydrolyzable matrix-forming compounds without non-hydrolyzable groups have in particular the general formula MX _b (formula (II)), where M is as defined above, X is as defined above in formula (I) and b corresponds to the valency of the element M (for example SiX ₄ , AIX ₃ ). The compounds can also be used in the form of pre-hydrolysates or condensates. However, the compounds just mentioned preferably make up no more than 20 mol%, in particular no more than 10 mol%, of the hydrolyzable monomeric compounds used overall. It is particularly preferred that no more than 4 mol% or 0 mol% of the hydrolyzable monomeric compounds used have no non-hydrolyzable substituent.

The coating composition further comprises at least one silver compound. These can be silver compounds soluble in water or organic solvents, for example AgNO ₃ , but the silver ions are preferably used in the form of complex compounds. The complexing agents are particularly preferably chelate complexing agents, ie bidentate or multidentate ligands, for example bidentate or six-dentate complexing agents. The silver compound which is soluble in the solvent is therefore in particular a complex of silver ions with complexing agents, in particular chelating complexing agents. Such silver complex compounds are formed, for example, by adding a silver compound and the complexing agent to a solvent, and the silver complex formed is then used in the form of this solution for the coating composition.

The silver (l) ions or the silver complex compounds can react under reducing conditions to form metal colloids. Examples of complexing agents which form a silver complex compound with silver (l) ions are halide ions such as iodide, bromide and in particular chloride (or the corresponding hydrohalic acids), thio compounds, thiocyano compounds, sugars such as pentoses and hexoses, for example Glucose, ß-dicarbonyl compounds, such as diketones, for example acetylacetonates, keto esters, for example acetoacetic acid esters and allylacetoacetate, ether alcohols, carboxylic acids, carboxylates, for example acetate, citrate or glycolate, betaines, diols, polyols, also polymers such as polyalkylene glycols, crown ethers, phosphorus compounds, 3-mercaptopropyltrimethoxysilane and 3-mer-captopropyltriethoxysilane, and amino compounds. Mercapto compounds, such as mercaptosilanes, amino compounds, such as aminosilanes, are particularly preferred. Mono-, di-, tri-, tetraamines and higher polyamines, used as complexing agents. Examples of organic amines are triethylene tetramine, diethylene tetramine, diethylene triamine and ethylene diamine. Examples of aminosilanes are 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and in particular 2-aminoethyl-3-aminopropyltrimethoxysilane (DIAMO), 2-aminoethyl-3-aminopropyltriethoxysilane, amino-hexyl-3-aminopropyltrimethoxysilane and 3-aminoxysilane. Silver diamine complex compounds are preferably used, complex formers with at least two amino groups which can form chelate complexes being particularly suitable. Of the amino complexing agents, the aminosilanes are particularly preferred.

The complexing agents are advantageously incorporated into the matrix that forms, in particular first in the form of a weak coordination bond with Ag ° that forms and then preferably in the form of a surface modification of the silver colloids formed, which can contribute to the stabilization of the silver colloids in the matrix. The surface modification by the complexing agent brings about an improved compatibility between the matrix and the surface-modified silver colloid. The complexing agents preferably also contain functional or non-functional groups which additionally promote the compatibility of the silver colloids with the matrix. These can be, for example, polar groups (e.g. hydroxyl, amino or carboxy groups) which promote compatibility with hydrophilic matrices or the corresponding binder, or nonpolar groups (e.g. alkyl groups or aryl groups) which promote compatibility with hydrophobic matrices or promote the appropriate binder, act.

The silver ions presumably undergo partial stabilization during the complexation, so that there is no spontaneous or daylight-induced reduction. Surprisingly, after reduction to Ag, for example by heat treatment or UV radiation with oxidation of existing organic compounds, a high mobility of Ag ° results, despite the surrounding complexing agents, so that colloids, for example of several thousand atoms, can form. When using a complexing agent, the ratio of Ag to complexing groups present is preferably 1: 0.1 to 1: 500, in particular 1: 1 to 1: 200. A bidentate complexing agent has, for example, 2 complexing groups. The complexing agents can at least partially also function as reducing agents for the silver ions. The solvents described below, for example alcohols or ketones, the by-products which form during the hydrolysis and condensation, for example alcohols, the hydrolyzable compounds used or a combination thereof, may also be considered as reducing agents.

Optionally, nanoscale inorganic solid particles can also be contained in the coating composition. This results in an improved mechanical strength (scratch resistance, hardness) of the coating. They generally have a particle size in the range from 1 to 300 nm or 1 to 100 nm, preferably 2 to 50 nm and particularly preferably 5 to 20 nm. This material can be used in the form of a powder, but is preferably in the form of a especially acidic or alkaline, stabilized sols used. The nanoscale inorganic solid particles can consist of any inorganic materials, but in particular they consist of metals or metal compounds such as (optionally hydrated) oxides such as ZnO, CdO, SiO ₂ , TiO ₂ , ZrO ₂ , CeO ₂ , SnO ₂ , Al ₂ O ₃ , ln ₂ O ₃ , La ₂ O ₃ , Fe ₂ O _3l CU ₂ O, Ta ₂ O ₅ , Nb ₂ O ₅ , V ₂ O ₅ , MoO ₃ or WO ₃ , chalcogenides, nitrides, phosphides, phosphates, silicates, Zirconates, aluminates or carbides. The nanoscale inorganic solid particles are preferably an oxide, hydrated oxide, nitride or carbide of Si, Al, B, Zn, Cd, Ti, Zr, Ce, Sn, In, La, Fe, Cu, Ta, Nb, V , Mo or W, particularly preferably of Si, Al, B, Ti and Zr. Oxides or oxide hydrates are particularly preferably used. Preferred nanoscale inorganic solid particles are SiO ₂ , Al ₂ O ₃ , ITO, ATO, AIOOH, ZrO ₂ and TiO ₂ . Examples of nanoscale SiO ₂ particles are commercially available silica products, for example silica sols such as the Levasile®, silica sols from Bayer AG, or pyrogenic silicas, for example the Aerosil products from Degussa. The nanoscale inorganic solid particles can be nanoscale inorganic solid particles modified with organic surface groups. The surface modification of nanoscale solid particles is a method known in the prior art, as described, for example, in WO 93/21127 (DE 4212633) and WO 98/51747 (DE 19746885).

The coating composition may contain further additives which are usually added in the art depending on the purpose and desired properties. Specific examples are organic compounds, crosslinking agents, solvents, organic and inorganic color pigments, dyes, UV absorbers, lubricants, leveling agents, wetting agents, adhesion promoters and starters. The starter can be used for thermally or photochemically induced crosslinking.

If necessary, organic compounds or crosslinking agents can be added to the coating composition. These can be organic monomers, oligomers or polymers which in particular contain at least two functional groups which can react with the functional groups of the hydrolyzable silanes used to form an organic crosslinking. It is e.g. B. aliphatic, cycloaliphatic or aromatic compounds. Organic compounds with at least two epoxy groups or at least two amino groups are preferably used. The use of the organic compounds can be advantageous, for example, for reasons of price. The organic compound is particularly used in an amount of not more than 30% by weight.

Usable organic epoxy compounds can, for example, of aliphatic, cycloaliphatic or aromatic esters or ethers or mixtures thereof, e.g. B. based on ethylene glycol, 1,4-butanediol, propylene glycol, 1,6-hexanediol, cyclohexanedimethanol, pentaerythritol, bisphenol A, bisphenol F or glycerol. Specific examples of organic compounds with at least two Epoxide groups are 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, bis- (3,4-epoxycyclohexyl) adipate, 1, 4-Butandiolglycidether, cyclohexanedimethanol diglycidyl ether, Glycerintriglycidether, Neopentylglycoldiglycidether, Pentaerythritpoly- glycidyl ether, 2-ethylhexyl glycidyl ether, 1, 6 -Hexanediol diglycidyl ether, propylene glycol coldiglycidyl ether, polypropylene glycol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, epoxy resins based on bisphenol A, epoxy resins based on bisphenol F and epoxy resins A / based on bisphenol F. Specific examples of organic compounds with at least two amino groups are 1,3-diaminopentane, 1,5-diamino-2-methylpentane, 1,4-diaminocyclohexane, 1,6-diaminohexane, diethylene diamine, triethylene tetramine or isophorone diamine. Of course, organic compounds that carry different functional groups can also be used.

Examples of suitable solvents are alcohols, preferably lower aliphatic alcohols, such as methanol, ethanol, 1-propanol, i-propanol and 1-butanol, ketones, preferably lower dialkyl ketones such as acetone and methyl isobutyl ketone, ethers, preferably lower dialkyl ethers, such as diethyl ether, dibutyl ether and THF, isopropoxyethanol, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate, butoxyethanol, chlorinated hydrocarbons such as chloroform, sulfoxides, sulfones, amides such as dimethylformamide and dimethylacetamide, and mixtures thereof. In principle, no solvent has to be used, especially if the hydrolysis of the hydrolyzable silanes to form alcohols, e.g. the above. However, a solvent can of course also be used.

When selecting the solvent, care should also be taken that the silver compound or silver complex compound contained in the coating composition is preferably soluble in the solvent. It is therefore often advantageous if a solvent or solvent mixture is used as the solvent, the water or another polar solvent, such as a C ₄ -C ₄ alcohol, for example methanol, ethanol, n-propanol, isopropanol, isobutanol or n Butanol, or acetone, includes. The silver complex compound can first be formed in a solvent and added as a solution to the coating composition, which may also contain another solvent.

The hydrolysis or (pre) condensation of the hydrolyzable compounds takes place in particular by the sol-gel process. The sol-gel process is a process familiar to the person skilled in the art. The hydrolysis or condensation is carried out either in the absence of a solvent or preferably in an aqueous or aqueous / organic reaction medium, if appropriate in the presence of an acidic or basic condensation catalyst such as HCl, HNO ₃ or NH ₃ . A partial hydrolysis or (poly) condensation of the hydrolyzable compounds (precondensate) is obtained. The degree of condensation, like the viscosity, can advantageously be adjusted, for example by means of the solvent. The liquid sol thus obtained is used to produce the coating composition. The silver compound, for example in the form of the complex compound, and the other components can then be added. Of course, the silver compounds, the complexing agent and the other components can also be added in any order before the hydrolysis or condensation.

The coating composition can be applied to the surface of the article in any conventional manner. -All common wet chemical coating processes can be used here. Examples are spin coating, (electro) dip coating, knife coating, spraying, spraying, spinning, drawing, spinning, casting, rolling, brushing, flood coating, film casting, knife casting, slot coating, meniscus coating, curtain coating, roller application or conventional printing processes such as screen printing or Flexoprint. The amount of coating composition applied is selected so that the desired layer thickness is achieved. For example, the procedure is such that dry layer thicknesses in the range from 1 to 15 μm and preferably 2 to 5 μm are obtained become. An advantage with the present invention is that the layer thicknesses can be chosen to be very variable.

After the coating composition has been applied to the article, drying may take place, e.g. at ambient temperature (below 40 ° C).

The optionally predried coating is subjected to a treatment with heat and / or radiation, the silver colloids being formed. It has been found that the silver colloids are surprisingly formed from the silver compounds even at low temperatures by the coating composition used according to the invention. The treatment can be either heat treatment or radiation. In a preferred embodiment, a combined treatment with heat and radiation takes place.

The formation of the silver colloids takes place in particular at temperatures below 200 ° C., in particular below 130 ° C., below 100 ° C. and even below 80 ° C. The silver colloids are e.g. with sole heat treatment in the range from 50 to 100 ° C., preferably from 60 to 80 ° C. or 70 to 80 ° C. The silver colloids can also be formed photochemically at ambient temperature only by irradiation. Actinic radiation, e.g. B. UV or laser radiation or electron beams used to form the silver colloids. UV radiation is particularly preferably used for the irradiation.

Irradiation is preferably carried out with simultaneous heat treatment. Irradiation, in particular UV irradiation, is preferably carried out at a temperature of 50 to 100 ° C., in particular 60 to 80 ° C. This combined treatment takes place, for example, over a period of 2 to 20 minutes. With a corresponding treatment without radiation, the duration of the treatment is extended by a factor of 1, 2 - 2. The generation of larger colloids, for example with 5 - 50 nm, 5 - 30 nm or 5 - 20 nm and in particular 10 - 20 nm diameter, is particularly important since these have a high long-term effect. Surprisingly, it has been shown that silver colloids with a diameter of, for example, 10 to 50 nm or 10 to 30 nm are formed particularly rapidly by UV radiation and heat treatment, even if the silver is added to the composition as a silver diamine complex. Without UV radiation, smaller Ag colloids are generated with the heat treatment (for example 5-20 nm). The silver colloids are formed to a certain extent in situ in the applied coating, the first (further) condensation and crosslinking reactions for the beginning curing of the coating optionally taking place simultaneously.

The amount of silver compound used in the coating composition depends on the desired concentration of silver colloids.

The coating composition to obtain the silver colloid-containing coating can be cured at temperatures below 300 ° C., preferably not more than 200 ° C. and in particular not more than 130 ° C. For the hardening, the heat treatment for the formation of the silver koiloids is preferably simply continued, that is to say at temperatures below 100 ° C. or below 80 ° C., for example at temperatures from 50 to 100 ° C. or 60 to 80 ° C. The curing time can be several hours, for example more than 2 hours, and more. Of course, the period shortens when the temperature increases. The formation of the silver colloids at low temperatures advantageously prevents the coating from hardening rapidly at the otherwise required higher temperatures, so that the colloids are given time to form. On the other hand, during the heat treatment to form the colloids, the first condensation processes and / or crosslinking reactions take place in the coating, which lead to an increased viscosity, which contributes to the stabilization of the silver colloids. If necessary, photochemical curing is also possible. A coating with an organically modified inorganic matrix is obtained, ie in addition to the inorganic matrix backbone, there are also organic side groups, which are optionally crosslinked with one another or via organic compounds, or contain other organic constituents. An increase in temperature makes it possible to reduce the organic proportion.

The process according to the invention now makes it possible to produce coating compositions which do not yet contain any silver colloids, to use them for coating substrates, in particular plastic substrates, and to treat silver colloids of the desired size and in the desired concentration of by treatment with heat and / or radiation to produce several wt .-%. For example, 0.1 to 40% by weight and in particular 1 to 10% by weight of silver colloids can be present in the finished coating. The coating can be obtained at low temperatures, so that temperature-sensitive substrates, e.g. temperature-sensitive plastics, can be coated with them without further notice. In addition, the coatings show very good elasticity behavior, so that even flexible substrates that deform easily (reversibly) under pressure can be coated.

The coated articles according to the invention show a strong biocidal action even over longer periods, especially in connection with liquid media. In particular, there are microbiocidal coatings on various substrates in combination with solutions with an effectiveness of several months. It has been shown that the use of such coatings on medication vials that come into contact with the eyes or nose prevents any bacterial contamination.

The objects coated according to the invention are therefore particularly suitable for disinfectant, preservative, cosmetic, pharmaceutical or medical purposes. Objects from the pharmaceutical or medical field, in particular containers for pharmaceuticals or objects or components that coming into contact with the human body and where sterility is required are preferred areas of application.

The following examples illustrate the invention without restricting it.

EXAMPLE 1

Production of a bactericide-coated substrate with thermal curing

a) Synthesis of the silver complex solution: 0.28 g of silver nitrate are dissolved in 30 g of ethanol (96%). After 30 minutes

13 g of isopropanol and 4 g of acetone are added and the mixture is stirred for a further 15 minutes. For complexation, 1.7 g of N- (2-aminoethyl-3-aminopropyl) trimethoxysilane are slowly added dropwise with vigorous stirring.

b) Synthesis of the coating composition:

0.03 mol of 3-glycidyloxypropyltrimethoxysilane (GPTMS) (7.09 g) are prehydrolyzed with 4.05 g of 0.01 N nitric acid for two hours at room temperature.

0.07 mol of dihydro-3- (3- (triethoxysilyl) propyl) -2,5-furanedione (GF 20) is initially introduced, and 0.07 mol of 3-aminopropyltrimethoxysilane (APTMS) is slowly added dropwise with ice cooling and vigorous stirring , The mixture is then diluted with 33.9 g of isopropoxyethanol (IPE) and stirred at room temperature for 30 minutes. 18.90 g of 0.01N nitric acid are added and the mixture is stirred at room temperature for 15 minutes. The mixture is then diluted with 43.3 g of IPE and the GPTMS pre-hydrolyzate is stirred in.

After stirring for 15 minutes, 28.38 g of the silver complex solution prepared in a) are added and the mixture is stirred for a further 15 minutes at room temperature. c) Application and treatment:

The application to the substrate can e.g. by diving, flooding or spinning. The layers are cured on glass for one hour at 130 ° C and on PE for 6 hours at 80 ° C.

EXAMPLE 2

Production of a bactericidal coated substrate under photochemical

Generation of silver colloids

0.03 mol of 3-glycidyloxypropyltrimethoxysilane (GPTMS) are prehydrolyzed with 4.05 g of 0.01N nitric acid for two hours at room temperature.

0.07 mol of dihydro-3- (3- (triethoxysilyl) propyl) -2,5-furandione (GF 20) is initially introduced and, while cooling with ice and vigorous stirring, 0.07 mol of 3-aminopropyltrimethoxysilane (APTMS) is slowly added dropwise , The mixture is then diluted with 33.9 g of isopropoxyethanol (IPE) and stirred for 30 minutes at room temperature. 18.90 g of 0.01N nitric acid are added and the mixture is stirred at room temperature for 15 minutes. The mixture is then diluted with 43.3 g of IPE and the GPTMS pre-hydrolyzate is stirred in.

After stirring for 15 minutes, 28.38 g of the silver complex solution prepared in Example 1a) are added and the mixture is stirred for a further 15 minutes at room temperature.

The coating composition can be applied to a substrate, for example, by dipping, flooding or spinning. To produce the Ag colloids, the coated substrate is exposed three times in a UV curing station from Beltron at half the power of both lamps at a speed of 0.8 m / min. After UV exposure, the layers on glass are cured for one hour at 130 ° C and on PE for 6 hours at 80 ° C. EXAMPLE 3

Production of a bactericide-coated substrate with a water-based system with photochemical generation of the silver colloids

0.5 mol of 3-glycidyloxypropyltriethoxysilane GPTES (139.21 g) are hydrolyzed with 1.5 mol of 0.1N hydrochloric acid (27 g) for 5 hours at room temperature. The ethanol formed is removed on a rotary evaporator at a bath temperature of 35 ° C. and 40 mbar. 463.0 g of Levasil 200 S (silica sol) are then stirred in at room temperature for 16 hours. 5 mol% (based on GPTES) of N- (2-aminoethyl-3-aminopropyl) trimethoxysilane (DIAMO) (5.56 g) are slowly added dropwise with vigorous stirring and the mixture is stirred in for one hour.

326.7 g (0.05 mol Ag) of the silver complex solution prepared in Example 1a) are added to the sol and stirred in for 30 minutes. The silver-containing sol is then filtered through a 5 μm filter.

Application of the coating composition to a substrate can e.g. by diving, flooding or spinning. To produce the silver colloids, the coated substrates are exposed three times in the UV curing station (type 60 / II) from Beltron at half the power of both lamps and a belt speed of 3 m / min. The exposed layers (e.g. on steel or aluminum) are hardened at 130 ° C for four hours.

Claims

1. Microbicide-coated article, in particular container, characterized in that a coating with an organically modified inorganic matrix containing silver colloids is present on at least part of the article, which coating can be obtained by applying a coating composition comprising a) a hydrolyzate or condensate based on at least one hydrolyzable silane with at least one non-hydrolyzable substituent and b) a silver compound, on the surface of the article and treatment with heat and / or radiation to form the silver colloid-containing coating.

2. Microbicide-coated article according to claim 1, characterized in that the article has a plastic surface at least on the coated parts or consists of plastic.

3. Microbicide-coated article according to claim 1 or 2, characterized in that the silver compound is a silver complex compound, in particular a silver diamine complex compound.

Microbicide-coated article according to claim 3, characterized in that the silver compound is a silver complex compound with 2-aminoethyl-3-aminopropyltrimethoxysilane, 2-aminoethyl-3-aminopropyltriethoxysilane, aminohex-yl-3-aminopropyltriethoxysilane or aminohexyl-3-aminopropilane trimethane.

Microbicide-coated article according to one of claims 1 to 4, characterized in that the coating composition is a hydrolyzate or condensate based on one or more silanes of the general formula (I)

R _a SiX _(4. _a) (I) comprises, in which the radicals R are identical or different and represent non-hydrolyzable groups, the radicals X are identical or different and represent hydrolyzable groups or hydroxyl groups and a is 1, 2 or 3.

6. Microbicide-coated article according to one of claims 1 to 5, characterized in that the coating composition is a hydrolyzate or condensate based

a) at least one hydrolyzable silane that has one or more epoxy groups on at least one non-hydrolyzable substituent, b) at least one hydrolyzable silane that has one or more amino groups on at least one non-hydrolyzable substituent, and c) at least one hydrolyzable silane that on has at least one non-hydrolyzable substituent one or more acid anhydride groups,

includes.

7. A method for producing a microbicidally coated article with a silver colloid-containing coating which has an organically modified inorganic matrix, in which a coating composition comprising a) a hydrolyzate or condensate based on at least one hydrolyzable silane with at least one non-hydrolyzable

Substituents and b) a silver compound, applied to at least part of the surface of the article and treated with heat and / or radiation to form the silver colloid-containing coating.

8. The method according to claim 7, characterized in that the treatment is carried out at a temperature below 200 ° C, in particular not more than 130 ° C.

9. The method according to claim 7 or 8, characterized in that the silver colloids are obtained by UV radiation and / or heat treatment at temperatures from 50 to 100 ° C.

10. Use of a microbicidal coated article according to one of claims 1 to 6 for disinfectant, preservative, cosmetic, pharmaceutical or medical purposes.

11. Use of a microbicidal coated article according to claim 10 for the storage of solids or liquids, in particular drugs.